The present invention relates to a silver halide photographic light-sensitive material (hereinafter simply referred to as a light-sensitive material or a photographic meterial), a mercapto compound, and a disulfide compound, and in more detail to a silver halide light-sensitive material, comprising said compound, which exhibits minimized fogging, and excellent pressure resistance, as well as excellent sensitivity.
Generally, various pressures are applied onto light-sensitive materials coated with silver halide emulsions. For example, sheet films such as graphic arts light-sensitive materials, and medical direct radiographic materials are manually handled which frequently results in being folded and curled. As noted above, when various pressures are applied onto photographic light-sensitive materials, silver halide grains are subjected to application of pressure through media such as gelatin as the binder of silver halide grains, and a plastic film as the support. When silver halide grains are subjected to application of pressure, variation of photographic performance results. Details are reported, for example, by K. B. Mather, J. Opt. Soc. Am., 38, 1054 (1948), P. Faelens and P. deSmet, Sci. et Ind. Phot., 24, No. 5, 178 (1954), P. Faelens, J. Phot. Sci., 2, 105 (1954), and others.
In addition, sought is further improvement of retaining performance of light-sensitive materials, particularly retardation of an increase in fogging during storage.
Camera light-sensitive materials are developed varying period of time from immediate to several months or one year after exposure. It is preferable that during such an elapse of time, fogging performance be maintained.
An objective of the present invention is to provide a silver halide photographic light-sensitive material, comprising mercapto compounds and disulfide compounds, which exhibits low fogging, excellent pressure resistance, and excellent sensitivity, and is to provide mercapto compounds as well as disulfide compounds.
The objective of the present invention has been achieved employing the embodiments below.
1. A silver halide photographic light-sensitive material comprising a support having thereon a light-sensitive silver halide emulsion layer comprising a compound represented by Formula,
Formula 1
Zxe2x80x94Sxe2x80x94X
wherein Z represents a group represented by Formula 1-2; X represents a hydrogen atom or Zxe2x80x94Sxe2x80x94, 
wherein A1, A2, A3, A4, and A5 each represent xe2x95x90Nxe2x80x94, xe2x95x90N(xe2x86x92O)xe2x80x94, or xe2x95x90CR91xe2x80x94, in which R91 represents a substituent, and at least two of A1, A2, A3, A4, and A5 are respectively xe2x95x90N(xe2x86x92O)xe2x80x94and xe2x95x90CR91xe2x80x94.
2. The photographic material of item 1, wherein the compound represented by Formula 1 is selected from the group of compounds represented by Formula 6 to Formula 14,
wherein R61, R71, R81, and R91 each represent a substituent; m6 represents 1 to 4; m7 and m8 represent an integer of 0 to 4; m9 represents an integer of 0 to 3; when m6, m7, m8 and m9 are 2 or more, R61, R71, R81, and R91 may be a different substituent and may bond to each other to form a condensation ring; A1, A2, A3, A4, and A5 each represent xe2x95x90Nxe2x80x94, xe2x80x94CR92, or xe2x95x90N(xe2x86x92O)xe2x80x94, and at least two of A1, A2, A3, A4, and A5 represent xe2x95x90Nxe2x80x94 or xe2x95x90N(xe2x86x92O)xe2x80x94, and at least one represents xe2x95x90N(xe2x86x92O)xe2x80x94; and R92 represents a substituent; Ra and Rb each represent an electron attractive group and may be the same or different, and p and q each represent integer of 1 to 4; R11, R12, R13, an R14 each represent a substituent; m11 represents an integer of 1 to 4; m12 and m13 each represent an integer of 0 to 4; m14 represents an integer of 0 to 3; A1, A2, A3, A4, and A5 each are the same as each of Formula 9.
3. The photographic material of item 2, wherein the compound represented by Formula 1 is selected from the group of compounds represented by Formula 6 to Formula 10, 
wherein R61, R71, R81, and R91 each represent a substituent; m6 represents an integer of 1 to 4; m7 and m8 represent 0 to 4; m9 represents an integer of 0 to 3; when m6, m7, m8 and m9 are 2 or more, R61, R71, R81, and R91 may be a different substituent and may bond to each other to form a condensation ring; A1, A2, A3, A4, and A5 each represent xe2x95x90Nxe2x80x94, xe2x95x90CRxe2x80x94, or xe2x95x90N(xe2x86x92O)xe2x80x94, and at least two of A1, A2, A3, A4, and A5 represent xe2x95x90Nxe2x80x94 or xe2x95x90N(xe2x86x92O)xe2x80x94, and at least one represents xe2x95x90N(xe2x86x92O)xe2x80x94; and R92 represents a substituent;
wherein Ra and Rb each represent an electron attractive group and may be the same or different, and p and q each represent an integer of 1 to 4.
4. The photographic material of item 2, wherein the compound represented by Formula 1 is selected from the group of compounds represented by Formula 11 to Formula 14.
wherein R11, R12, R13, and R14 each represent a substituent; m11 represents an integer of 1 to 4; m12 and m13 each represent an integer of 0 to 4; m14 represents an integer of 0 to 3; and A1, A2, A3, A4, and A5 each are the same as each of Formula 9.
5. The photographic material of item 3, wherein each R61, R71, R81, and R91 in Formula 6 to Formula 9 represents a group which promotes adsorption onto silver halide grains.
6. The silver halide light-sensitive material of item 1,
wherein the compound is contained in an amount of 1xc3x9710xe2x88x927 to 1xc3x9710xe2x88x921 mole per mole of Ag.
7. The silver halide light-sensitive material of item 3, wherein the compound is represented by Formula 10,
wherein Ra and Rb each represent an electron attractive group and may be the same or different, and p and q each represent an integer of 1 to 4.
8. The photographic material of item 3, wherein the compound is represented by Formula 6,
wherein R61 represent a substituent and m6 represents an integer of 1 to 4, when m6 is 2 or more, R61 may be a different substituent and may bond to each other to form a condensation ring.
9. The photographic material of item 3, wherein the compound is represented by Formula 7,
wherein R71 represent a substituent and m7 represents an integer of 0 to 4, when m7 is 2 or more, R71 may be a different substituent and may bond to each other to form a condensation ring.
10. The silver halide light-sensitive material of item 3, wherein the compound is represented by Formula 8,
wherein R81 represent a substituent and m8 represents an integer of 0 to 4, when m8 is 2 or more, R81 may be a different substituent and may bond to each other to form a condensation ring.
11. The photographic material of item 3, wherein the compound is represented by Formula 9, 
wherein A1, A2, A3, A4, and A5 each represent xe2x95x90Nxe2x80x94, xe2x95x90CRxe2x80x94, or xe2x95x90N(xe2x86x92O)xe2x80x94, and at least two of A1, A2, A3, A4, and A5 represent xe2x95x90Nxe2x80x94 or xe2x95x90N(xe2x86x92O)xe2x80x94, and at least one represents xe2x95x90N(xe2x86x92O)xe2x80x94; and R92 represents a substituent;
12. The photographic material of item 1, wherein the emulsion is subjected to reduction sensitization.
13. The photographic material of item 3, wherein the emulsion contains a tabular silver halide grain.
14. A photographic material comprising a compound represented by Formulas 2 to 5, 6-2, and 7-2.
wherein X1 represents xe2x80x94NR21xe2x80x94 or xe2x80x94Oxe2x80x94; X2, X3, and X4 each represents xe2x95x90CR22xe2x80x94 or xe2x95x90Nxe2x80x94; both R21 and R22 represent a hydrogen atom or a substituent; X1, X2, X3, and X4 may form a condensation ring with each other, however, all of X1, X2, X3, and X4 are not a nitrogen atom; Y1, Y2, Y3, Y4, and Y5 each represent xe2x95x90Nxe2x80x94 or xe2x95x90CR31xe2x80x94, however, any one of Y1, Y3 and Y5 is not xe2x95x90Nxe2x80x94; Q represents a group of atoms necessary for forming a 5-membered or 6-membered heterocyclic ring comprising at least one of xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94N less than , xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94, or NR31COxe2x80x94, wherein R31 represents a hydrogen atom or a substituent; G represents an oxygen atom and a sulfur atom; W represents xe2x80x94Sxe2x80x94Sxe2x80x94C(xe2x95x90G)xe2x80x94 as well as a group of atoms necessary to form a 5-membered or 6-membered ring, and may have a substituent which may form a ring along with W; R62 represents an alkyl group having at least 2 carbon atoms, an aryl group, a cycloalkyl group, a hydroxy group, a carboxy group, a nitro group, a trifluoromethyl group, an amido group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a carbonyloxy group, a cyano group, a bromine atom, an iodine atom, a fluorine atom, an alkoxy group, an aryloxy group, a sulfonyl group, a sulfonamido group, a sulfamoyl group, an amino group, an alkylamino group, or a hydroxyamino group, m62 represents an integer of 1 to 4, and when m62 is at least 2, R62 may be a different group and may bond to each other to form a condensation ring; R72 represents a substituent, and m72 represents an integer of 1 to 4; R81 represents a substituent and m8 represents an integer of 0 to 4; A1, A2, A3, A4, and A5 each represent xe2x95x90Nxe2x80x94, xe2x95x90CR92xe2x80x94 or xe2x95x90N(xe2x86x92O)xe2x80x94, at least two of A1, A2, A3, A4, and A5 represent xe2x95x90Nxe2x80x94 or xe2x95x90N(xe2x86x92O)xe2x80x94, and at least one represents xe2x95x90N(xe2x86x92O)xe2x80x94; and R91 and R92 each represent a substituent, and m9 represents an integer of 0 to 3.
The present invention will now be detailed.
In Formula 1, Z represents a group represented by Formula 1-2; X represents a hydrogen atom or Zxe2x80x94Sxe2x80x94; A1, A2, A3, A4, and A5 in Formula 1-2 each represent xe2x95x90Nxe2x80x94, xe2x95x90N(xe2x86x92O)xe2x80x94, or xe2x95x90CR91xe2x80x94, in which R91 represents a substituent, and at least two of A1, A2, A3, A4, and A5 are respectively xe2x95x90N(xe2x86x92O)xe2x80x94, and xe2x95x90CR91xe2x80x94, that means at least one of A1, A2, A3, A4, and A5 represents xe2x95x90N(xe2x86x92O)xe2x80x94, and at the same time at least one of the rest represents xe2x95x90CR91xe2x80x94. Substituents represented by R91 include an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group, a stearyl group, a dodecyl group, an eicocyl group, a dococyl group, and an oleyl group); a cycloalkyl group (for example, a cyclopropyl group and a cyclohexyl group); an aryl group (for example, a phenyl group, a p-tetradecanyloxyphenyl group, an o-octadecanylaminophenyl group, a naphthyl group, and a hydroxyphenyl group); a hydroxy group; a carboxy group; a nitro group; a trifluoromethyl group; an amido group (for example, an acetamide group and a benzamido group); a carbamoyl group (for example, a methylcarbamoyl group, a butylcarbamoyl group, and a phenylcarbamoyl group; an alkyloxycarbonyl group (for example, an ethyloxycarbonyl group and an isopropyloxycarbonyl group); an aryloxycarbonyl group (for example, a phenyloxycarbonyl group); a carbonyloxy group (for example, a methylcarbonyloxy group, a propylcarbonyloxy group, and a phenylcarbonyloxy group); a cyano group; a halogen atom (a chlorine atom, a bromine atom, a iodine atom, and a fluorine atom); an alkoxy group (for example, a methoxy group, and a butoxy group); an aryloxy group (for example, a phenoxy group); a sulfonyl group (for example, a methanesulfonyl group and a p-toluenesulfonyl group); a sulfonamido group (for example, a methanesulfonamido group, a dodecylsulfonamido group, and a p-toluenesulfonamido group); a sulfamoyl group (for example, a methylsulfamoyl group and a phenylsulfamoyl group); an amino group; an alkylamino group (for example, an ethylamino group, a dimethylamino group, and a hydroxyamino group). When there are at least two xe2x95x90CR91xe2x80x94, R91 may be different from each other, and a plurality of xe2x95x90CR91xe2x80x94 may bond to each other to form a condensation ring.
In Formula 2, X1 represents xe2x80x94NR21xe2x80x94 or xe2x80x94Oxe2x80x94; X2, X3, and X4 each represents xe2x95x90CR22xe2x80x94 or xe2x95x90Nxe2x80x94; both R21 and R22 represent a hydrogen atom or a substituent (for example, an alkyl group such as a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group, a stearyl group, a dodecyl group, an eicocyl group, a dococyl, and an oleyl group; a cycloalkyl group such as a cyclopropyl group, and a cyclohexyl group; and an aryl group such as a phenyl group, a p-tetradecanyloxypenyl group, an o-octadecanylaminophenyl group, a naphthyl group, and a hydroxyphenyl group) may form a condensation ring with X1, X2, X3, and X4, and however, all of X1, X2, X3, and X4 are not xe2x95x90Nxe2x80x94.
In Formula 3, Y1, Y2, Y3, Y4, and Y5 each represent xe2x95x90Nxe2x80x94 or xe2x95x90CR31xe2x80x94 wherein R31 represent a hydrogen atom or a substituent (for example, an alkyl group such as a methyl group, an ethyl group, an isopropyl group, a cyclohexyl group, a hydroxyethyl group, a stearyl group, a dodecyl group, an eicocyl group, a dococyl, and an oleyl group; a cycloalkyl group such as a cyclopropyl group, and a cyclohexyl group; and an aryl group such as a phenyl group, a p-tetradecanyloxypenyl group, an o-octadecanylaminophenyl group, a naphthyl group, and a hydroxyphenyl group. However, any one of Y1, Y3 and Y5 is not xe2x95x90Nxe2x80x94.
In Formula 4, Q represents a group of atoms necessary for forming a 5-membered or 6-membered heterocyclic ring comprising at least one of xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94N less than , xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94, or xe2x80x94NR31COxe2x80x94, wherein R31 represent a hydrogen atom or a substituent (for example, an alkyl group such as a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group, a stearyl group, a dodecyl group, an eicocyl group, a dococyl, and an oleyl group; a cycloalkyl group such as a cyclopropyl group, and a cyclohexyl group; and an aryl group such as a phenyl group, a p-tetradecanyloxypenyl group, an o-octadecanylaminophenyl group, a naphthyl group, and a hydroxyphenyl group.
In Formula 5, G represents an oxygen atom and a sulfur atom, and W represents a group of atoms necessary to form a 5-membered or 6-membered ring along with xe2x80x94Sxe2x80x94Sxe2x80x94C(xe2x95x90G)xe2x80x94and may have a substituent which may form a ring along with W. Said rings include an aryl group such as a phenyl group, a p-tetradecanyloxypenyl group, an o-octadecanylaminophenyl group, a naphthyl group, and a hydroxyphenyl group. Said substituents include an alkyl group such as a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group, a stearyl group, a dodecyl group, an eicocyl group, a dococyl, and an oleyl group; a cycloalkyl group such as a cyclopropyl group and a cyclohexyl group; a hydroxy group; a carboxy group; a nitro group; a trifluoromethyl group; an amido group such as acetamido group, and a benzamido group; a carbamoyl group such as a methylcarbamoyl group, a butylcarbamoyl group, and a phenylcarbamoyl group; an alkyloxycarbonyl group such as an ethyloxycarbonyl group and an isopropyloxycarbonyl group; an aryloxycarbonyl group such as a phenyloxycarbonyl group; a carbonyloxy group such as a methyl carbonyloxy group, a propylcarbonyloxy group, and a phenylcarbonyloxy group; a cyano group; a halogen atom such as a chlorine atom, bromine atom, an iodine atom, and a fluorine atom; an alkoxy group such as a methoxy group, an ethoxy group, and a butoxy group; an aryloxy group such as a phenoxy group; a sulfonyl group such as a methanesulfonyl group and a p-toluenesulfonyl group; a sulfonamido group such as a methanesulfonamido group, a dodecylsulfonamido group, and a p-toluenesulfonamido group; a sulfamoyl group such as a methylsulfamoyl group and a phenylsulfamoyl group; an amino group; an alkylamino group such as an ethylamino group, dimethylamino group, and a hydroxyamino group.
In Formula 6, R61 represents a substituent. Said substituents include an alkyl group such as a methyl group, an ethyl group, an isopropyl group, a hydroxyethyl group, a stearyl group, a dodecyl group, an eicocyl group, a dococyl, and an oleyl group; a cycloalkyl group such as a cyclopropyl group, and a cyclohexyl group; an aryl group such as a phenyl group, a p-tetradecanyloxypenyl group, an o-octadecanylaminophenyl group, a naphthyl group, and a hydroxyphenyl group; an aryl group such as a phenyl group, a p-tetradecanyloxypenyl group, an o-octadecanylaminophenyl group, a naphthyl group, and a hydroxyphenyl group, a hydroxy group; a carboxy group; a nitro group; a trifluoromethyl group; an amido group such as acetamido group and a benzamido group; a carbamoyl group such as a methylcarbamoyl group, a butylcarbamoyl group, and a phenylcarbamoyl group; an alkyloxycarbonyl group, such as an ethyloxycarbonyl group and an isopropyloxycarbonyl group; an aryloxycarbonyl group such as a phenyloxycarbonyl group; a carbonyloxy group such as a methylcarbonyloxy group, a propylcarbonyloxy group, and a phenylcarbonyloxy group; a cyano group; a halogen atom such as a chlorine atom, bromine atom, an iodine atom, and a fluorine atom, an alkoxy group such as a methoxy group, an ethoxy group and a butoxy group; an aryloxy group such as a phenoxy group; a sulfonyl group such as a methanesulfonyl group and p-toluenesulfonyl group; a sulfonamido group such as a methanesulfonamido group, a dodecylsulfonamido group, and a p-toluenesulfonamido group; a sulfamoyl group such as a methylsulfamoyl group, and a phenylsulfamoyl group; an amino group; an alkylamino group such as an ethylamino group, dimethylamino group, and a hydroxyamino group. When m6 is 2 or more, R61 may be a different group and may combine with each other to from a condensation ring.
In Formula 6-2, R62 represents a substituent. Said substituents include an alkyl group having at least 2 carbon atoms such as an ethyl group, an isopropyl group, a cyclohexyl group, a hydroxyethyl group, a stearyl group, a dodecyl group, an eicocyl group, a dococyl, and an oleyl group; an aryl group such as a phenyl group, a p-tetradecanyloxypenyl group, an o-octadecanylaminophenyl group, a naphthyl group, and a hydroxyphenyl group; an aryl group such as a phenyl group, a p-tetradecanyloxypenyl group, an o-octadecanylaminophenyl group, a naphthyl group, and a hydroxyphenyl group; a hydroxy group; a carboxy group; a nitro group; a trifluoromethyl group; an amido group such as acetamido group and a benzamido group; a carbamoyl group such as a methylcarbamoyl group, a butylcarbamoyl group, and a phenylcarbamoyl group; an alkyloxycarbonyl group, such as an ethyloxycarbonyl group and an isopropyloxycarbonyl group; an aryloxycarbonyl group such as a phenyloxycarbonyl group; a carbonyloxy group such as a methylcarbonyloxy group, a propylcarbonyloxy group, and a phenylcarbonyloxy group; a cyano group; a halogen atom such as a chlorine atom, bromine atom, an iodine atom, and a fluorine atom; an alkoxy group such as a methoxy group, an ethoxy group, and a butoxy group; an aryloxy group such as a phenoxy group; a sulfonyl group such as a methanesulfonyl group and p-toluenesulfonyl group; a sulfonamido group such as a methanesulfonamido group, a dodecylsulfonamido group, and a p-toluenesulfonamido group; a sulfamoyl group such as a methylsulfamoyl group and a phenylsulfamoyl group, an amino group; an alkylamino group such as an ethylamino group, a dimethylamino group and a hydroxyamino group. When m62 is 2 or more, R62 may be a different group and may bond to each other to form a condensation ring.
In Formula 7, R71 represents the same as R61.
In Formula 7-2, R72 represents the same as R61.
In Formula 8, R81 represents the same as R61.
In Formula 9, R91 represents the same as R61.
In Formula 10, Ra and Rb each represent an electron attractive group which includes a carboxy group; a nitro group; a trifluoromethyl group; a carbamoyl group such as a methylcarbamoyl group, a butylcarbamoyl group, and a phenylcarbamoyl group; an alkyloxycarbonyl group such as an ethyloxycarbonyl group and an isopropyloxycarbonyl group; an aryloxycarbonyl group such as a phenyloxycarbonyl group; a cyano group; a halogen atom such as a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom; a sulfonyl group such as a methanesulfonyl group, and a p-toluenesulfonyl group; a carbonyloxy group such as a methylcarbonyloxy group and a propylcarbonyloxy group; an alkylcarbonyl group such as a methylcarbonyl group and a phenylcarbonyl group.
In Formula 11, R11 represents the same as R61.
In Formula 12, R12 represents the same as R61.
In Formula 13, R13 represents the same as R61.
In Formula 14, R14 represents the same as R61.
Agents which promote adsorption onto silver halide grains include groups derived from cyclic or chain thioethers (for example, dimethyl sulfide, methyl sulfide, methyl phenyl sulfide, and thiocrown ethers), groups derived from aliphatic mercaptans (for example, groups derived from methylmercaptan, and propylmercaptan), groups derived from aromatic mercaptans (for example, thiophenol, and thionaphthol), and, groups derived from cyclic or chain thioamides, groups derived from cyclic or chain thioureids, groups derived from heterocyclic mercaptans (when a nitrogen atom is adjacent to a carbon atom which is bonded to an xe2x80x94SH group, said groups are the same as cyclic thioamido groups which is in the relationship of tautomers, and the specific examples of said groups are the same as those listed above), groups derived from azoles capable of forming silver imide, groups derived from nitrogen-containing aromatic cyclic quaternary salts (for example, N-methylpyridinium salt, and N-ethylquinolium salt). Of these, preferred are groups derived from thioamide, thioureido, aromatic mercaptans, heterocyclic mercaptans or azoles capable of forming silver imide, but more preferred are groups derived from heterocyclic mercaptans or azoles capable of forming silver imide.
Specific examples of groups, derived from heterocyclic mercaptans and derived from azoles capable of forming silver imide, include those derived from heterocyclic mercaptans such as mercaptotetrazole, 3-mercapto-1,2,4-triazole, 2-mercapto-1,3,4-oxadiazole, 2-mercapto-1,3,4-thisdiazole, 2-mercaptoimidazole, 2-mercapto-1,3-oxazole, 2-mercapto-1,3-thiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 2-mercaptopyridine, 2-mercaptopyrimidine, and mercaptotriazine, and derived from azoles capable of forming silver imide such as benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, tetraazaindene, indazole, and purine. Of these, preferred are groups derived from mercaptotetrazole, 3-mercapto-1,2,4-triazole, 2-mercapto-1,3,4-oxadiazole, 2-mercapto-1,3,4-thiadiazole, 2-mercaptobenzimidazole, 2-mercaptobenzozazole, 2-mercaptobenzothiazole, 2-mercaptopyrimidine, mercaptotriazine, benzotriazole, and triazole, however more preferred are groups derived form mercaptotetrazole, 3-mercapto-1,2,4-triazole, 2-mwercapto-1,3,4-thiadiazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, benzotriazole, tetrazole, and still more preferably employed are groups derived from mercaptotetrazole, 2-mercapto-1,3,4-thiadiazole and benzotriazole Spefici examples of compounds of the present invention will now be illustrated below. However, the present invention is not limited to these examples. 
Synthesis examples of the compounds of the present invention will now be described.
 less than Synthesis of Compound 6-2 greater than 
5.0 g of Compound 6-2a were dissolved in 50 ml of dichloromethane, and 6.2 g of urea peroxide were added. The resulting mixture was cooled to 0xc2x0 C. and 13.2 g of trifluoroacetic anhydride were slowly added dropwise. The resulting mixture was stirred for 30 minutes as it was, and then heated to room temperature. When the reaction was completed, an aqueous sodium sulfite solution was added to decompose excess peroxides. The resulting mixture was poured into a 0.5 mole/liter aqueous hydrochloric acid solution. Subsequently, extraction was carried out utilizing dichloromethane, and the resulting extract was washed with an aqueous sodium hydrogencarbonate solution, and then dried utilizing magnesium sulfate. Then, solvents were removed under reduced pressure. The resulting suspension was washed with acetonitrile and filtered, whereby 4.5 g (a yield of 82 percent) of Compound 6-2b were obtained. The structure was identified utilizing NMR and mass spectra.
Then, 4.0 g of Compound 6-2b were dissolved in 50 ml of ethanol and 2.6 g of sodium hydrosulfide were added. The resulting mixture was heated to 100xc2x0 C. while stirring. After the completion of the reaction, the solvent was removed under reduced pressure, and the resulting residue was dissolved in water. The resulting solution was acidified utilizing acetic acid, whereby precipitates were formed. The resulting precipitates were collected by filtration, and 3.5 g (a yield of 89 percent) of Compound 6-2c was obtained. The structure was identified utilizing NMR and mass spectra.
Subsequently, 3.0 g of Compound 6-2c were subjected to suspension in water and then heated to 40xc2x0 C. Subsequently, 2.3 g of a 30 percent aqueous hydrogen peroxide solution were added dropwise while maintaining a temperature no higher than 50xc2x0 C. The reaction mixture was stirred at 45xc2x0 C. After setting aside the resulting reaction mixture over night in a refrigerator at 5xc2x0 C., crystals were collected employing filtration and then washed with chilled methanol, whereby 2.3 g (a yield of 78 percent) of Compound 6-2 were obtained. The structure was identified utilizing NMR and mass spectra.
 less than Synthesis of Compound 7-2 greater than 
5.0 g of Compound 7-2a were dissolved in 50 ml of dichloromethane, and 6.3 g of urea peroxide were added. The resulting mixture was cooled to 0xc2x0 C. whereupon 13.2 g of trifluoroacetic anhydride were slowly added dropwise. The resulting mixture was stirred for 30 minutes as it was, and then heated to room temperature. When the reaction was completed, an aqueous sodium sulfite solution was added to decompose excess peroxides. The resulting mixture was poured into a 0.5 mole/liter aqueous hydrochloric acid solution. Subsequently, extraction was carried out utilizing dichloromethane, and the resulting extract was washed with an aqueous sodium hydrogencarbonate solution, and then dried utilizing magnesium sulfate. Solvents were then removed under reduced pressure. The resulting product was washed with acetonitrile and filtered, whereby 4.4 g (a yield of 80 percent) of Compound 7-2b were obtained. The structure was identified utilizing NMR and mass spectra.
Then, 4.0 g of Compound 7-2b were dissolved in 50 ml of ethanol and 2.6 g of sodium hydrosulfide were added. The resulting mixture was heated to 100xc2x0 C. while stirring. After the completion of the reaction, the solvent was removed under reduced pressure, and the resulting residue was dissolved in water. The resulting solution was acidified utilizing acetic acid, whereby precipitates were formed. The resulting precipitates were collected by filtration, and 2.9 g (a yield of 89 percent) of Compound 7-2c was obtained. The structured was identified utilizing NMR and mass spectra.
Subsequently, 2.0 g of Compound 7-2c were subjected to suspension in water and then heated to 40xc2x0 C. Subsequently, 2.0 g of a 30 percent aqueous hydrogen peroxide solution were added dropwise while maintaining a temperature no higher than 50xc2x0 C. The resulting mixture was stirred at 45xc2x0 C. After setting aside said resulting reaction mixture overnight in a refrigerator at 5xc2x0 C., crystals were collected employing filtration and then washed with chilled methanol, whereby 2.3 g (a yield of 80 percent) of Compound 7-2 were obtained. The structure was identified utilizing NMR and mass spectra.
 less than Synthesis of Compound 8-3 greater than 
5.0 g of Compound 8-3a were dissolved in 50 ml of dichloromethane, and 5.8 g of urea peroxide were added. The resulting mixture was cooled to 0xc2x0 C. and 13.2 g of trifluoroacetic anhydride were slowly added dropwise. The resulting mixture was stirred for 30 minutes as it was, and then heated to room temperature. When the reaction was completed, an aqueous sodium sulfite solution was added to decompose excess peroxides. The resulting mixture was poured into a 0.5 mole/liter aqueous hydrochloric acid solution. Subsequently, extraction was carried out utilizing dichloromethane, and the resulting extract was washed with an aqueous sodium hydrogencarbonate solution, and then dried utilizing magnesium sulfate. Solvents were then removed under reduced pressure. The resulting product was washed with acetonitrile and filtered, whereby 4.6 g (a yield of 85 percent) of Compound 8-3b were obtained. The structure was identified utilizing NMR and mass spectra.
Then, 4.0 g of Compound 8-3b were dissolved in 50 ml of ethanol and 2.4 g of sodium hydrosulfide were added. While stirring, the resulting mixture was heated to 100xc2x0 C. After the completion of the reaction, the solvent was removed under reduced pressure, and the resulting residue was dissolved in water. The resulting solution was acidified utilizing acetic acid, whereby precipitates were formed. The resulting precipitates were collected by filtration, and 2.7 g (a yield of 68 percent) of Compound 8-3c was obtained. The structure was identified utilizing NMR and mass spectra.
Subsequently, 2.5 g of Compound 8-3c were subjected to suspension in water and then heated to 40xc2x0 C. Subsequently, 1.7 g of a 30 percent aqueous hydrogen peroxide solution were added dropwise while maintaining a temperature no higher than 50xc2x0 C. The resulting mixture was stirred while maintaining 45xc2x0 C. After setting aside the resulting reaction mixture overnight in a refrigerator at 5xc2x0 C., crystals were collected employing filtration and then washed with chilled methanol, whereby 2.1 g (a yield of 87 percent) of Compound 8-3 were obtained. The structure was identified utilizing NMR and mass spectra.
 less than Synthesis of Compound 9-1 greater than 
5.0 g of Compound 9-la were dissolved in 50 ml of dichloromethane, and 8.6 g of urea peroxide were added. The resulting mixture was cooled to 0xc2x0 C. and 18.3 g of trifluoroacetic anhydride were slowly added dropwise. The resulting mixture was stirred for 30 minutes as it was, and then heated to room temperature. When the reaction completed, an aqueous sodium sulfite solution was added to decompose excess peroxides. The resulting mixture was poured into a 0.5 mole/liter aqueous hydrochloric acid solution. Subsequently, extraction was carried out utilizing dichloromethane, and the resulting extract was washed with an aqueous sodium hydrogencarbonate solution, and then dried utilizing magnesium sulfate. Then, any remaining solvents were removed under reduced pressure. The resulting product was washed with acetonitrile and filtered, whereby 4.8 g (a yield of 84 percent) of Compound 9-1b were obtained. The structure was identified utilizing NMR and mass spectra.
Then, 4.0 g of Compound 9-1b were dissolved in 50 ml of ethanol and 3.4 g of sodium hydrosulfide were added. The resulting mixture was heated to 100xc2x0 C. while stirring. After the completion of the reaction, the solvent was removed under reduced pressure, and the resulting residue was dissolved in water. The resulting solution was acidified utilizing acetic acid, whereby precipitates were formed. The resulting precipitates were collected by filtration, and 3.3 g (a yield of 85 percent) of Compound 9-1c were obtained. The structure was identified utilizing NMR and mass spectra.
Subsequently, 3.0 g of Compound 9-1c were subjected to suspension in water and then heated to 40xc2x0 C. Subsequently, 3.3 g of a 30 percent aqueous hydrogen peroxide solution were added dropwise while maintaining a temperature no higher than 50xc2x0 C. The resulting mixture was stirred while maintaining 45xc2x0 C. After setting aside the resulting reaction mixture over night in a refrigerator at 5xc2x0 C., crystals were collected employing filtration and then washed with chilled methanol, whereby 2.7 g (a yield of 91 percent) of Compound 9-1 were obtained. The structure was identified utilizing NMR and mass spectra.
It is possible to synthesize other compounds employing the same or analogous methods.
The added amount of the compounds represented by Formulas 1 through 14 of the present invention is not particularly limited. However, when added to light-sensitive silver halide emulsion layers, the added amount is preferably in the range from 1.0xc3x9710xe2x88x927 to 1.0xc3x9710xe2x88x921 mole per mole of AgI of the layer to be added, and is more preferably in the rang from 1.0xc3x9710xe2x88x926 to 5.0xc3x9710xe2x88x923 mole.
It is also possible to add the compounds represented by Formulas 1 through 14 of the present invention in the form of a solid or a solution. When added in the form of a solution, said compounds may be dissolved in water, in water-soluble solvents, or in mixtures thereof, and the resulting solution may be added. Or said compounds may be subjected to emulsion dispersion, and the resulting dispersion may then be added. When dissolved in water, it is possible to adjust the pH to a high or low value so as to enhance the solubility, and then the resulting solution may be added. Two or more compounds may also be employed in combination.
As reduction sensitization preferably employed in the present invention, it is possible to select any of the methods in which reducing agents, known in the art, are added to silver halide emulsions, in which silver halide grains are subjected to growth or ripening at a low pAg of 1 to 7, which is called silver digestion, or in which silver halide grains are subjected to growth or ripening at a high pH of 8 to 11, which is called high pH ripening. Further, two or more methods may be employed in combination. The light-sensitive materials including the compound represented by Formula 1 are resistive to latent-image regression.
A method, in which reduction sensitizers are added, is preferable one in the point in which it is possible to precisely control the level of reduction sensitization. Reduction sensitizers, known in the art, include stannous salts, amines, polyamine acids, hydrazine derivatives, formamidinesulfinic acid, silane compounds, and borane compounds. In the present invention, it is possible to employ reduction sensitizers selected from those known in the art and to employ those in combination of two or more types. Preferable reduction sensitizers include stannous chloride, urea dioxide, and dimethylaminoborane. It is necessary to determine the added amount of reduction sensitizers, depending on the emulsion production conditions. However, the added amount is suitably in the range from 10xe2x88x927 to 10xe2x88x923 mole per mole of silver halide.
It is also possible to preferably employ ascorbic acid and derivatives thereof as the reduction sensitizers employed in the present invention. It is permissible to dissolve reduction sensitizers in water, alcohols, glycols, ketones, esters, or amides, and to add the resulting composition during grain formation, prior to or after chemical sensitization. Said reduction sensitizers may be added during any of the emulsion preparation processes. However, any method, in which addition is carried out during grain growth, is particularly preferred. Reduction sensitizers may also be previously charged into a reaction vessel. However, it is preferable that the addition is carried out at the optimal time during grain growth.
Further, reduction sensitizers may be added in advance to an aqueous water-soluble silver salt or water-soluble alkali halide solution, and grains may be formed employing these aqueous solutions.
Further, any method is preferred in which, along with grain formation, a reduction sensitizer solution is added several times after dividing said solution, or continuously added over a long period of time.
Silver halide grains incorporated into the silver halide emulsion, which has undergone reduction sensitization, preferably employed in the present invention, may have regular crystal structures such as cube, octahedron, tetradecahedron, or irregular crystal forms such as sphere and a tabular form. Of these structures, tabular grains are preferred. Grains having an optional ratio of (100) plane to (111) plane may also be employed. Further, grains having complexes of these crystal forms may be employed, and grains having various crystal forms may be mixed.
Tabular silver halide grains, as described in the present invention, refer to grains having one twin plane or at least two parallel twin planes. The aspect ratio of said grains is commonly 2 or more, and is preferably from 3 to 12.
In the present invention, the average grain diameter of silver halide grains is preferably from 0.2 to 10 xcexcm, is more preferably from 0.3 to 7.0 xcexcm, and is most preferably from 0.4 to 5.0 xcexcm.
In the present invention, employed as silver halide photographic emulsions may be optional emulsions such as polydispersed emulsions having a wide grain size distribution and monodispersed emulsions having a narrow grain size distribution. However, the monodispersed emulsions are preferably employed.
In the present invention, it is possible that in said silver halide photographic emulsions, optionally employed as silver halides may be silver iodobromide, silver iodochlorobromide, or silver iodochloride. However, silver iodobromide and silver iodochlorobromide are particularly preferred.
In the present invention, the average silver iodide content ratio of silver halide grains contained in the silver halide photographic emulsion is preferably from 1 to 40 mole percent, and is more preferably from 2 to 20 mole percent.
Preferably employed as silver halide grains incorporated into the silver halide photographic emulsion, which is preferably employed in the present invention, may be core/shell type grains. Said core/shell type grains, as described herein, refer to those comprised of a core, and a shell covering said core. Said shell is comprised of one or more layers. The silver iodide content ratio of said core and said shell is preferably different from each other.
It is possible to prepare the silver halide emulsion preferably employed in the present invention, employing various methods known in the art.
Namely, it is possible to employ a single-jet method, a double-jet method, a triple-jet method, or a fine silver halide grain supplying method, and combinations thereof. Further, it is possible to employ a method in combination in which the pH as well as the pAg in a liquid phase, in which silver halide is formed, is controlled while matching the growth rate of silver halide grains.
It is also possible to employ a seed emulsion to produce silver halide photographic emulsions. When said seed emulsion is employed, silver halide grains of said seed emulsion may have regular crystal structures such as a cube, octahedron and tetradecahedron, or irregular crystal forms such as a sphere or a tabular form. Of these grains, grains having an optional ratio of the (100) plane to the (111) plane may be employed. Further, grains having complexes of these crystal forms may also be employed, and grains having various crystal forms may be mixed. In the present invention, when said tabular silver halide grains are employed, silver halide grains in the employed seed emulsion are preferably those having a twin plane, and twinned silver halide grains having two parallel twin planes facing each other are particularly preferred.
In the present invention, if a seed emulsion is employed or not employed, it is possible to apply the methods known in the art to determine conditions for silver halide nucleation and ripening.
During the production of silver halide photographic emulsions, it is possible to employ silver halide solvents known in the art. Examples of said silver halide solvents include (a) organic thioethers described in U.S. Pat. Nos. 3,271,157, 3,531,289, and 3,574,628; Japanese Patent Publication Open to Public Inspection Nos. 54-1019, and 54-158917; and Japanese Patent Publication No. 58-30571; (b) thiourea derivatives described in Japanese Patent Publication Open to Public Inspection Nos. 53-82408, 55-29829, 57-77736 and others; (c) silver halide solvents having a thiocarbonyl group interposed between an oxygen or a sulfur atom and a nitrogen atom, as described in Japanese Patent Publication Open to Public Inspection No. 53-144319; (d) imidazoles described in Japanese Patent Publication Open to Public Inspection No. 54-100717; (e) sulfites; (f) thiocyanates; (g) ammonia; (h) ethylenediamines substituted by a hydroxyalkyl group, described in Japanese Patent Publication Open to Public Inspection No. 57-196228; (i) substituted mercaptotetrazoles described in Japanese Patent Publication Open to Public Inspection No. 57-202531; (j) water-soluble bromides; and (k) benzimidazole derivatives described in Japanese Patent Publication Open to Public Inspection No. 58-54333.
It is possible to apply any of an acidic emulsion method, a neutral emulsion method, and an ammonia emulsion method to the production of silver halide photographic emulsions.
In the production of silver halide photographic emulsions, halide ions and silver ions may be simultaneously mixed, or any one of them may be mixed with any others. Further, taking into account the critical growth rate of silver halide crystals, it is possible to add halide ions and silver ions successively, or simultaneously, while controlling the pAg and pH in the reaction vessel. The halide composition of silver halide grains may be varied utilizing a conversion method at any of the stages during the formation of silver halide.
In the production of silver halide photographic emulsions, during the nucleation process and/or the nucleus growth process of silver halide grains, employing at least one selected from a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt (including its complex salts), a rhodium salt (including its complex salts), an iron salt or other VIII group metal salts (including their complex salts), metal ions may be added so that said metal ions may be incorporated into the interior and the surface of silver halide grains.
In the present invention, it is possible to employ twinned silver halide crystals having two parallel twin planes facing each other, but in this case, the silver halide grain is preferably tabular. The twinned crystals, as described above, are silver halide crystals having at least one twin plane in one grain. The classification of twin crystal structures is described in detail in Klein and Moiser, Photographisches Korrespondenz, Volume 99, page 99 and Volume 100, page 57.
When tabular silver halide grains are employed in the present invention, at least 50 percent of the total projection area of silver halide grains incorporated into the silver halide emulsion subjected to reduction sensitization, which is preferably employed in the present invention, is preferably comprised of tabular silver halide grains, at least 60 percent of the same is more preferably comprised of tabular silver halide grains, and at least 80 percent is still more preferably comprised of tabular silver halide grains.
When tabular silver halide grains are employed in the present invention, the ratio of tabular silver halide grains having two twin planes parallel to the major plane is preferably at least 60 percent in terms of the number of silver halide grains, is more preferably at least 70 percent, and is still more preferably at least 80 percent.
During the production of silver halide emulsions, it is possible to employ materials capable of forming a protective colloid as the dispersion medium, and gelatin is preferably employed.
In the present invention, when gelatin is employed as the dispersing medium, it is possible to employ alkali processed gelatin, acid processed gelatin, or deionized gelatin. Methods for producing such gelatin is detailed in Arthur Veis, xe2x80x9cThe Macromolecular Chemistry of Gelatinxe2x80x9d, Academic Press, 1964, and others.
Further, listed as materials capable of functioning as forming protective colloid, other than gelatin, may be, for example, gelatin derivatives, graft polymers of gelatin with other polymers, proteins such as albumin, and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfuric acid ester; sugar derivatives such as sodium alginate; and starch derivatives; synthetic or semi-synthetic hydrophilic homopolymers and copolymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-n-vinylpyrrolidone, polyacrylic acid, polyacrylamide, polymethacrylic acid, polyvinyl imidazole or polyvinyl pyrazole.
Silver halide grains in silver halide photographic emulsions preferably possess dislocation lines in their interior. Positions, in which said dislocation lines are located, are not particularly limited. However, said dislocation lines are preferably located near the exterior surface, edges, or tops of silver halide grains. The ratio of positions, into which said dislocation lines are introduced, is preferably at least 50 percent with respect to the total silver amount of silver halide grains, and is more preferably from 60 to 80 percent. The ratio (by number) of silver halide grains having at least 5 dislocation lines per grain is preferably at least 30 percent, is more preferably at least 50 percent, and is still more preferably at least 80 percent. Further, in each case, the number of dislocation lines per grain is preferably at least 10, is more preferably at least 20, and is still more preferably at least 30.
During production of silver halide photographic emulsions, it is possible to employ oxidizing agents known in the photographic art. Listed as oxidizing agents are, for example, hydrogen peroxide (as an aqueous solution) and addition products thereof, such as H2O2, NaBO2, H2O2xe2x80x943H2O, 2Na2CO3xe2x80x943H2O2, Na4P2O7xe2x80x94H2O2, and 2Na2SO4xe2x80x94H2O2xe2x80x942H2O, and peroxyacid salts such as K2S2O3, K2C2O3, K4P2O3, K2[Ti (O)2C2O4]xe2x80x943H2O, peracetic acid, ozone, and thiosulfonic acid compounds.
During production of silver halide emulsions, reduction sensitization may be carried out in combination of said oxidizing agents.
During production of silver halide photographic emulsions, it is possible to carry out desalting during formation of silver halide grains, or after forming silver halide grains, for the purpose of preventing physical ripening or removing unnecessary salts. Desalting may be carried out, for example, employing the method described in Research Disclosure (hereinafter referred to as RD) Item 17643 Sect. II.
In order to remove unnecessary water-soluble salts from flocculated compositions or emulsions after physical ripening, a noodle washing method may be employed in which gelatin is gelled. Alternatively, it is possible to employ a flocculation method, employing inorganic salts, anionic surface active agents, anionic polymers (for example, polystyrene sulfonic acid), or gelatin derivatives (for example, acylated gelatin and carbamoyled gelatin).
Employed as other desalting methods may be desalting utilizing membrane separation described in xe2x80x9cKagaku Kogaku Binran (Handbook of Chemical Engineering)xe2x80x9d, 5th Edition, pages 924 to 954, edited by Kagakukogaku Kyokai and published by Maruzen, and others.
Methods described RD Volume 102 Item 10208 and Volume 131 Item 13122; Japanese Patent Publication Nos. 59-43727 and 62-27008; Japanese Patent Publication Open to Public Inspection Nos. 62-113137, 57-209823, 59-43727, 62-113137, 61-219948, 62-23035, 63-40137, 63-40039, 3-140946, 2-172816, 2-172817, and 4-22942, and others may be applicable to said membrane separation.
In the production of silver halide photographic emulsions, it is possible to select suitable conditions other than those described above while referring to Japanese Patent Publication Open to Public Inspection Nos. 61-6643, 61-14630, 61-112142, 62-157024, 62-18556, 63-92942, 63-151618, 63-163451, 63-220238, and 63-311244; RD Volume 365 Item 36544, Volume 367, Item 36736, and volume 391 Item 39121; and others.
Additives, which are employed to constitute color photographic materials employing silver halide emulsions, are described in RD Items 17643, 18716 and 308119. Tables 1 and 2 show reference sites of concerned compounds.
When light-sensitive color photographic materials are constituted employing silver halide emulsions, it is possible to employ various types of couplers. Specific examples of said couplers are described in the aforementioned RD. Table 3 shows reference sites of concerned couplers.
Additives, which are employed to constitute light-sensitive color materials employing silver halide emulsions may be added employing the dispersion method described in RD Item 308119 XIV. When light-sensitive color materials are constituted employing silver halide emulsions, it is possible to use supports described in RD Item 17643 page 28, RD Item 18716 pages 647 to 648, and RD Item 308119 XIX.
Light-sensitive color photographic materials, employing silver halide emulsions, may be provided with auxiliary layers such as filter layers or interlayers described in RD Item 308119 VII-K.
Light-sensitive color photographic materials, employing silver halide emulsions, may be constituted utilizing various layer configurations such as a conventional layer order, a reversed layer order or a unit constitution as described in RD Item 308119 VII-K.
Silver halide emulsions may be applied to various types of color photographic materials, represented by color negative film for general use or cinema use, color reversal film for slide or television applications, color paper, color positive film, and color reversal paper and various types of black-and-white light-sensitive materials such as monochromatic negative film, microfilm, and X-ray film.
Light-sensitive color photographic materials employing silver halide emulsions may be subjected to photographic processing employing conventional methods described in RD Item 17643 pages 28 to 29, RD Item 18716 page 615, and RD Item 308119 XIX.